Heat treatment of solid carboncontaining materials



July 19, 1955 G. H. PALMER ETAL 2,713,590

CONTAINING MATERIALS HEAT TREATMENT OF' SOLID CARBON- Filed OGC. 28,1948 4 Sheets-Sheet l July 19, 1955 G. H. PALMER ET AL 2,713,590

HEAT TREATMENT 0F SOLID CARBON- CONTAINING MATERIALS Filed Oct. 28, 19484 Sheets-Sheet 2 FIG.2

JNVEN'J'ORS EE0/TG5 H PALMER B) ,URL/ZA /v ALEX/1 NUE/T .ATTENEY July19, 1955 G. H. PALMER ETAL l2,713,590

CONTAINING MATERIALS HEAT TREATMENT 0F SOLID CARBON- Filed Oct. 28, 19484 Sheets-Sheet 5 El EMM@ July 19, 1955 G. H. PALMER ET-AL 2,713,590

HEAT TREATMENT OF SOLID CARBON-CONTAINING MATERIALS Filed Oct. 28, 19484 Sheets-Sheet 4 N m 2 G N q) I E N l/)J 03 uw: Q fa i lq Lo N 3 CD m LQ0 N Q Se N LL Y 5% 5% N N N N N INVENTORE EEO/:'51: PALMER Bgm/ZA NALEX/1 /vz/EF? .A TTDEZVE'Y 'the production of which Unit . StatesPatent Patented July 19, 195.3

HEAT TREATMENT F SOLID CARBN- CNTAINNG MATERIALS George H. Palmer,Fatevi/ood, N. 5., and Cruzan Alexu ander, Jackson Heights, N. Y.,assignors to The M. W. Kellogg Company, Jersey City, N. I., acorporation of Delaware Application ctoher 28, 1948, Serial No. 57,08816 Claims. (Cl. Z50-449.6)

It has been known that coal may be treated with `oxygen and steam in areaction zone at relatively high temperatures to convert the coal tohydrogen and carbon monoxide, which products are useful for variouspurposes such as fuel or as a feed gas for the synthesis of organiccompounds. In general, the coal or coke is contacted with steam in areaction Zone at a temperature above about l000 F. The operatingconditions employed are such that a substantial proportion of the steamreacts with coal to produce hydrogen and carbon monoxide, products isfavored by high temperature.

It has been proposed to maintain the required temperature for thegasification of the coal by simultaneously introducing oxygen with thesteam into the gasification zone. The temperature of reactionrecommended was not always that best suited for the production of themaximum amount of carbon monoxide. For example, relatively lowtemperatures were proposed as being practical because of the economicadvantage gained in the saving of oxygen and in order to obtain a fuelgas having methane which increased the heating value of the resultinggas. Working at these lower temperatures would inevitably result in theproduction of some carbon dioxide at the expense of carbon monoxide. Theproduction of carbon dioxide is favored at lower temperatures by boththe steam-coal reaction and the oxygen-coal reaction. Carbon dioxidethus produced would constitute product gas, It is much which may forreasons costly operation. to be desired, therefore, to provide a processoperate at the relatively or minimizes the amount of carbon dioxideproducedl companied by the minimum amount of carbon dioxide formation.

A further used in a suspended condition.

Another object of this invention is to provide a method for removal andseparation of ash and like undesirable material from a process for thegasification of carboncontaining solid materials.

Au object of this invention is to provide a gasification process inwhich volatile components of the solid carboncontaining materials may berecovered.

A further object is to provide a gasification process which issubstantially proposed processes.

Various other objects and advantages of the present invention willbecome apparent to those skilled in the art from the accompanyingdescription and disclosure.

According to the improved process of this invention, carbon-containingsolid material and any accompanying separate reaction zone,carbon-containing solid material, any accompanying carbon dioxide andoxygen are reacted under optimum exothermic conditions such that ismaintained at the desired level by liberation of the sensible heat ofthe coal circulated.

C sensible heat of the coal circulated thereto. Conveniently,unconvcrted coal or coke from the endothermic rcaction zone is returnedto the exothermic reaction zone for further conversion thereof; freshcoal being added to the process at the desired point in the system,either intermittently or continuously.

The preferred method of operation is by the use of the so-calledfluidized technique in which the coal is in a finely-divided form andpresent in the reaction zone in a conventional uidized pseudo-liquidcondition. Gaseous reactants and products are passed upwardly through amass of finely-divided coal at a suiiicient velocity to maintain thecoal in such a lluidized condition whereby the finely-divided particlesof coal circulate throughout a dense phase in the lower portion of thereaction zone. The use of the uidized technique also has the advantageof substantially uniform temperature conditions within the iluidizedmass because of the high heat transfer rate between the gas and solidparticles. Fluidized coal or coke is circulated between the reactionzones by means of conventional methods, such as by the use of aeratedstandpipes of sufficient length to overcome pressure drops or by the useof solids pumps, such as a Fuller-Kinyon pump.

In this type of operation the coal is used in a finelydivided form,preferably a major proportion of the coal has a particle size less thanabout 250 microns. The finely-divided condition of the coal may beobtained 'oy crushing and grinding large pieces of coal in suitableequipment, such as a ball mill, or by explosion pulverization.

It is believed that the present invention may be best described byreference to the accompanying drawings which show the inventive featuresof the present invention as applied, for example, to the synthesis oforganic compounds and to the production of a fuel of high heating value.

Figure 1 of the drawings is a diagrammatic illustration in elevation ofan arrangement of apparatus for thc synthesis of organic compoundsembodying the present invention in which the coal in the gasificationstep is maintained in a fluidized pseudo-liquid dense phase condition inboth the exothermic and endothermic reaction zones.

Figure 2 of the drawings is a modification of the operating techniqueshown in Figure 1 and illustrates an arrangement of apparatus for theoperation of the invention in which the coal is carried in the gaseousreactants in a relatively less dense condition than the conventionaldense phase of Figure l.

Figure 3 of the drawings is a diagrammatic illustration in elevation ofan arrangement of apparatus for the production of a fuel gas of highheating value cmbodying teachings of the present invention in whichfinely-divided coal in the gasification step is maintained in apseudo-liquid dense phase condition.

Figures 4 and 5 illustrate modifications of the present invention forthe introduction of fresh coal into the system and the removal of ashfrom the system.

Referring with particularity to Figure l of the drawings, anoxygen-containing gas, such as substantially pure oxygen or enrichedair, is passed by means of conduit 4 through a conventional heatexchanger 2S to conduit 6. Coal or coke is introduced into conduit 6 andmixed with the oxygen-containing gas, and the resulting mixture ispassed to partial combustion chamber 7, which comprises a conventionalcylindrical chamber having a refractory lining. Oxygen is passed upwardthrough a mass of finely-divided coal or coke in chamber 7 at a velocitysufficient to maintain the finely-divided solids in a fluidizedpseudo-liquid condition characterized by an interface S between a lowerdense phase and an upper relatively dilute phase. Sufficient oxygen isutilized in proportion to the mass of coal or coke that a uniformtemperature between about 1800 and about 2000 F.

is maintained in chamber 7' at approximately atmospheric pressure. Asuitable oxidation temperature in chamber 7 is about 1900 F. Under theconditions utilized in chamber 7 coal is converted to a major proportionof carbon monoxide and a minor proportion of carbon dioxide. However,under the temperature conditions employed in chamber 7 a minimum amountof carbon dioxide is produced, in some instances less than about one percent of the product gases. An eiiluent gas containing carbon monoxideand some entrained ash and unburncd coal or coke is passed to a solidsseparator ll which may comprise a conventional cyclone separator. lfdesired, a cyclone separator or ceramic filters may be positioned withinchamber '7 to at least partially remove e entrained coal and ash. Sincethe ash is a relatively lighter material than the coal, the solidsWithdrawn from reactor 7 through conduit 9 contain a higher proportionof ash than present in the dense phase. Hence, permitting solids to passoverhead from reactor 7 and separating them from the eflluent inseparator 1i is a convenient and effective manner of preventing thebuild-up of ash in the system. Solids thus separated are withdrawn fromseparator 11 through conduit 26.

Finely-divided coal and/ or coke at a relatively high temperature iswithdrawn from the dense phase of chamber through a conduit or standpipe13 and introduced into a gas stream consisting essentially of steampassing through conduit 16. An aerating or stripping gas, such as steam,carbon dioxide, or recycle gas from the synthesis step to be discussedfurther hereinafter, may be introduced into conduit or standpipe 13 foraerating and/ or stripping the solid particles therein. Steam isintroduced into the system through conduit 16 and may be by-passedthrough conduit 17 to heat exchanger 28 for supcrheating. The resultingmixture of steam and solids withdrawn from chamber 7 are passed throughconduit 16 to a gasification chamber i8, which comprises a conventionalcylindrical reaction chamber similar to that of chamber '7.Alternatively or additionally to coal introduced into the system throughconduit 6, fresh coal may be introduced into conduit 16 by means ofconduit 24. This may be a particularly desirable location forintroducing coal, since the coal is contacted at this point at atemperature somewhat lower than that existing in chamber 7. Volatilecomponents are distilled from the coal at a temperature at which thetendency for their decomposition is minimized. The relatively lowtemperature at this point also reduces the tendency of the fresh coal tofuse and the finely-divided particles to agglomerato or stick together.

The finely-divided coal in chamber 18 is maintained in a luidizedcondition characterized by an interface 19 between a lower' dense phaseand an upper dilute phase similar to that described with respect tochamber 7. For the production of a gas of optimum composition withrespect to hydrogen and carbon monoxide by the steamcoal reaction, thetemperature of chamber 18 is maintained between about 1500 and aboutl700 F. at atmospheric pressure by regulating the temperature andquantity of the solids circulated from chamber '7 to chamber 1S. Underthe optimum conditions maintained in chamber' 18 steam is reacted withthe coal or col'e to produce hydrogen and carbon monoxide with a minimumformation of carbon dioxide, methane and water vapor, usually less than5 per cent, in the product. An efuent comprising hydrogen and carbonmonoxide and entrained coal or coke and ash is removed from chamber i8through conduit 2i. and is passed to separator il as previouslydiscussed. Ash and coal are separated from the effluent and removed fromseparator ii. through conduit 26. As in the case of chamber 7, cycloneseparator or ceramic filters may be positioned within chamber 18, inaddition to or substitution for, the case may warrant, separator 1l forremoving at least a portion of the entrained solids from the cfiluent.Unconverted coal gage may be employed without departing from the scopeof this invention. Pressures below about 150 pounds per square inch gageare preferred, however. At elevated pressures somewhat highertemperatures are necessary for the respective reaction zones in order toprevent the increased production of undesirable by-products. In general,partial combustion chamber 7 is operated at a temperature correspondingto a temperature between 1800 and about 2000" F. for atmosphericpressure operations, and gasification chamber 13 is operated at atemperature corresponding to about 1300 to about 1700 F. for atmosphericpressure operations. Excess coal is employed in the system to supplysuiiicient heat carrier material for transferring a portion of theexothermic heat of reaction from chamber 7 to chamber 18.

A gaseous efiiuent comprising hydrogen and carbon monoxide in a ratio ofabout 0.5:1 to about 2:1 at a temperature usually above about 1500 F.when producing a synthesis feed gas is removed from solids separatorheat exchanger 28 the synthesis feed gas passes of finely-dividedcatalyst such of the Periodic Table, for example reduced iron or cobalt,under suitable operating 1 conditions for the conversion of hydrogen andcarbon monoxide to normally liquid organic compounds comprisinghydrocarbons and oxygenated organic compounds. When using reduced ironas the catalyst a temperature between about 550 employed, and preferablya pressure corresponding subthan, the pressure em- Higher pressures, upto as high as 700 pounds per square inch gage, may be employed. Whenpressures are employed in synthesis reactor 31 which are above thepressure employed in the gas-making step, a suitable compressor must beused. The mass of finely-divided catalyst in reactor 31 is maintained ina fluidized condition characterized by an interface 32 between a lowerdense phase and an upper relatively dilute phase. Catalyst is withdrawnfrom the dense phase of reactor 31 through conduit or standpipe 34 andpassed through a conventional catalyst cooler 36 and reintroduced intoconduit 29. The temperature of synthesis reactor 31 may be controlledwithin relatively narrow limits by removal of exothermic heat ofreaction by means of catalyst cooler 36. Catalyst may be withreactor 31by means not shown.

Synthesis reactor 31 may be cooled also by indirect cooling meanspositioned within the dense phase, if desired. A suitable vaporizing orcooling liquid may also be introduced directly into the dense phase forcooling purposes. A cyclone separator or iilters may be posiand about750 F. is f tioned within or externally of reactor 31 to remove e11-trained catalyst from the reaction eiiluent.

A reaction effluent comprising hydrogen, carbon dioxide, methane anaccumulators or fractional distillation Columns with suitable auxiliaryequipment for the separation and recovery of the products of theprocess.

hydrocarbons and oil-soluble oxygenated'chemicals, are removed fromrecovery unit 38 through conduit 41. Uncondensed vapors, such ashydrogen, carbon dioxide and methane, are removed from recovery unit 38through conduit 42 and may be passed directly to conduit 17 forintroduction into gasification chamber 18. ferrcd to introduce methaneinto 1?, so that it can be reformed with steam therein to producehydrogen and carbon monoxide.

All or a portion of the jected to conditions of temperature and pressureto the carbon dioxide. Gases substantially free from carbon dioxide andcontaining methane are removed from abmay be'passed, if desired, throughconduit 47 to conduit 42 for circulation to gasification chamber 1S.

or carbon dioxide rich gases are preferably passed to combustion chamber7 in which optimum conditions exist for the conversion of carbon dioxideto carbon monoxide.

is returned from absorption unit 44 through conduit 47 to conduit 42.

In order to prevent the build-up of nitrogen in the system, particularlywhen enriched air is used as the oxygen-containing gas, a portion of thevapors in conduit 42 or conduit 47 are vented to the atmosphere. Airitself may be used as the oxygen-containing gas in line 4 withoutdeparting from the scope of this invention, and under such circumstancesa large proportion of the vapors in conduit 42 is vented to theatmosphere.

In the operation of Figure l described above the sole source of heat isthe partial combustion of coal in chamber 7. However, external heatingmeans may be provided in addition to the partial combustion of coal forproducing heat. Such external means may comprise preheating furnaces forthe steam and/or oxygen-containing gas. A catalytic material orheat-carrying material, such as an ore, may be used in combination withthe coal in chambers 7 and 18 without departing from the scope of thisinvention. For example, an iron ore containing magnetite may be admixedwith the coal introduced into conduit 6 or introduced tirough conduit2d. The magnetite promotes the production ol hydrogen and carbonmonoxide and also serves as a heat-carrying material for the lioW ofheat from partial combustion chamber 7 to gasification chamber X8.

Various methods may be utilized to obtain the iinelydivided condition ofthe coal for use in a iluioized process described with respect to Figurel. rl'he coal may be crushed lirst in a jaw Crusher and then ball-milledto the desired size. Alternatively, the coul may be introduced into astream ol steam which is injected into the system by reducing thepressure at least 50 to lo() pounds, thereby pulverizing the coal byexplosion pulverizatiou (expansion of the steam in the pores of thecoal).

Figure 2 ol the drawings is a moditication of the invention in whichgasilication chamber l ot .Figure l is operated with a sulilicientlyhigh linear gas velocity therein that the net movement of the coal is inthe direction of liow of the gas stream passing therethrough. as aresult of the gas velocity. The description ot Figure 2 will be brief,since the operating conditions may be substantially thc same as thosedescribed with respect to Figure l, and it should be understood that theproduct gas obtained the-refr ni may be utilized for the synthesis oforganic compounds in the manner described with respect to Figure l.Steam passes through conduit 6l and heat exchanger 82 to gasilicationchamber 62, which comprises an elongated conduit generally of relativelysmall diameter as compared to the chamber lll of Figure l. The steam inconduit el picks up hot coal or colte from conduit 76 and the resultingmixture is converted to hydrogen and carbon monoxide in chamber 62.Additionally', steam may be introduced longitudinally at spacedintervals along chamber 62 through conduits 66, 67, and 63, as shown, toaid in maintaining the desired concentration of steam at any particularpoint in chamber 62. The velocity of the gases in chamber 62 ispreferably above 5 feet per second, usually between 8 and about 40 feetper second, depending on such factors as particle size and density,reaction conditions, etc., such that the iinely-divided coal or collemoves in the direction of the Flowing gases and may at very highvelocities travel at substantially the same rate as the gases. Theconcentration of the coal in the gases is much less than theconcentration of coal in a conventional pscudoliquid dense phase, whichis usually 20 pounds per cubic foot of gas or greater, and for thisreason stiel-:ing and agglomeration of the coal or coke is minimized.The concentration of finely-divided solids is generally in the range oiabout l to about l() pounds per cubic toot of gas. Unconverted coal orcoke, ash, hydrogen, carton monoxide, and steam are Withdrawn fromgasification chamber 62 through conduit 63 and are passed at the aboverelatively high velocity to separator 64. Separator' 64 may con'ipr aconventional settling zone, a cyclone separator, or the like, forseparation of unconverted coal or eolie and ash from the gasificationeffluent. Since the gasification effluent in conduit (3 is at arelatively low temperature because or endothermic reaction in chamber62, it may bc desirable to introduce fresh coal into the process intoconduit 63 through conduit 69. ln this manner the fresh coal contactsthe gases of the process at the minimum temperature whereby the valuablevaporizable products of the process are distilled Without substantialcracking thereof. Moreover, since the stream of gases in conduit 6E isat a relatively high velocity and the solids are Well dispersed therein,the tendency for thc fresh coal to agglomerate and stick is minimized.lt is therefore a particular feature of this invention to introducefresh coal into the high velocity eiliuent stream from chamber 62 andmaintain the coal therein long enough to substantially completelydistill vaporizable components from the fresh coal. Thus, the

ti length of conduit 63 may be adapted to achieve sufficient holdingtime for distillation of the fresh coal.

Separated coal is passed from separator 64 into partial combustionchamber 72 by gravity. Oxygen is introduced into partial combustionchamber 72 at a plurality of points spaced longitudinally along chamber72, such as by means of conduits 73 and 74, in order to minimize hotspots or local overheating. In partial combustion chamber 72 coal orcoke is converted to carbon monoxide and carbon dioxide accompanied byliberation of heat. Coal and/or coke is withdrawn from gasificationchamber 72 at a relatively high temperature by means of standpipe 76.The quantity of oxygen and the shape of chamber 72 is suoli that asuiiiciently high upward gas velocity is maintained therein to maintainthe iinelydivided coal or coke in a iiuidized pseudo-liquid conditionsimilar to that described With respect to combustion chamber 7 of Figurel. The velocity may be sufficiently low that little, if any, circulationof the solids in the dense phase is obtained. In this modilication thesolids liow substantially countercurrently to upflowing gases. A portionof the finely-divided coal and/or coke is withdrawn from chamber 72through conduit 78 to prevent the build-up of ash in the system. Ash maybe sep arated from unconverted coal or coke withdrawn through conduit 73and the separated unconverted material returned to the process, ifdesired.

ln order to produce a maximum amount of hydrogen and methane from thecoal, fresh coal is preferably introduced directly into separatorthrough conduit '77. ln this manner the fresh coal is contacted with thehot gases from partial combustion chamber 72, which gases are at arelatively high temperature favorable to the conversion of the volatilecomponents of the coal to hydrogen and methane.

An acrating or stripping gas may be introduced into standpipe 76 throughconduit 83. Such aerating or stripping gas. may comprise recycle gases,carbon dioxide, or oxygen. il/hen s 'A ping is eilectcd in conduit 76 toremove occluued cf on monoxide, a relatively larger proportion of gas isintroduced into conduit 33 than when mere aerating is effected inconduit 76 to assure free low ol solids therethrough.

A gaseous eliiuent comprising hydrogen, carbon monoxide, carbon dioxide,l unconverted steam is removed from separator 64.l through conduit 8land is passed through heat exchanger 82. The effluent gases in conduitSl may be passed to a synthesis reactor, as described in Figure l, ormay be usal as a, fuel gas. When the coal contains valuablevolatilizable components and is introduced into the system throughconduit 69 the eti'luent gases in conduit 8l are jassed to a coolingsystem for condensation and recovery ol water and valuable organiccomponents of the coal, such as tars, naphthalcne, anthraccne, bcnzol,toluol. phenol, crcsol, Xylol, and normally gaseous nd liquidhydrocarbons, as well as some nitrogen and sulfur compounds.

Figure 3 of 'the drawings, illustrating another embodiment of thepresent invention, diagrammatically shows in elevation an arrangement olapparatus for the production of a fuel gas of high heating value inaccordance with the teachings of this invention. A gaseous streamcomprising oxygen or a mixture of oxygen and other gases, such as carbondioxide, is passed through conduit 91 to a partial combustion chamber92. Recycle coal is introduced into the "as stream in conduit 91 bymeans of conduit or standpip W2 and is carried to chamber 92. Asexplained in the discussion of chamber' 7 of Figure l, gasificationchamber 62 is operated at optimum exothcrmic conditions for theconversion of coal or coke to carbon monoxide accompanied by theliberation of heat. The preferred temperature range for gasificationchamber 92 is between about 1800 and about 2000 F. The gas is passedupward through chamber 92 at a velocity sulcient to suspend the coal ina so-called pseudo-liquid dense phase in which the fine solid particlescirculate throughout the dense phase. A gaseous effluent comprisingcarbon monoxide and containing ash and in some cases entrained coal orcoke is passed through conduit 93 and a conventional heat exchanger orcooler 94 and thence to a solids separator 96. The gaseous effluent fromchamber 92 is cooled by heat exchanger 9d. Solids separator 96 maycomprise any conventional type of separating means for separating solidsfrom gases, such as an enlarged settling zone or a cyclone separator.

Cyclone separators or filters may be'positioned Within chamber 92 to atleast remove a portion of the entrained solids carried with the gaseouseffluent. the use of cyclone separators within chamber 92, additionalmeans, such as separator 96, 1s usuallyv employed to remove additionalentrained solids, particularly ash.

Coal and/or coke at a relatively high temperature is removed fromcombustion chamber 92 by means of standpipe 97 and passed to conduit 98.Water is introduced into conduit 98 and passes through a heater or heatformation of carbon dioxide. tage of the present process, therefore,that the oxidation reaction and the steam-coal reaction can becarriedout in separate reaction zones. Thus, the additional carbondioxide which would be formed bythe oxygen-coal reacmonoxide togetherwith small proportions of carbon dioxide.

A gaseous effluent comprising hydrogen, carbon monoxide, carbon dioxide,methane, and entrained ash and in some instances coal or coke is removedfrom chamber 101 through conduit 103 and may be passed directlyseparation of the solids from the effluent.

In the preferred modification of Figure 3, fresh coal is introduceddirectly into chamber 101 by means of contain also volatile componentsof the coal and is passed through conduit 104 to a separator 106 whichcomprises a cooler and an accumulator for condensing liquid productsfrom the effluent. These valuable liquid products, which in mostinstances are the volatile compassed from separator 106 through conduit108 to a conventional carbon dioxide absorber 109.

In carbon dioxide absorber 109, the gaseous stream Substantially all ofthe carbon dioxide is removed from the eiuent in absorber 109. A gasconsisting essentially of hydrogen, carbon monoxide and methane isremoved from absorber 109 and passed through conduit 111 to separator 96to be combined with the effluent from cham ber 92. A high heating valuegas comprising hydrogen,

product of the process.

In most instances the removal of carbon dioxide from duit 118. Desorbedcarbon dioxide is removed from desorption zone 114 through conduit 116and may be chamber 92. The carbon dioxide thus produced in gasiflcationchamber 101 is converted to carbon monoxide in 101 to at least partiallyremove entrained coal or coke and ash from the reaction effluent.

Ash and coal separated from the effluents by separator 96 are removedtherefrom through conduit 119 for disposal or recirculation to either orboth chambers 92 and 101.

Fresh coal is introduced into the process from hopper 127 through eitherconduit 128 or conduit 129. Coal recover the maximum amount of Volatilecomponents without the decomposition thereof. Unconverted coal and/orcoke is removed from gasification chamber 101 through a standpipe 102for circulation to combustion chamber 92, as previously discussed.

Upon continuous introduction of coal into the process pletely burn thecoal. Oxygen, together with an inert gas if desired, is passed througheiongated flows 1n the direction of flow of the gas stream, it isoxygen, carbon dioxide and carbon monoxide at a relatively hightemperature are removed from separator 124 and passed through conduit126 and heat exchanger 99 to combustion chamber 92. The effluent fromreactor 123 may supply the necessary oxygen and heat for the conversionof coal in chamber 92 to carbon monoxide. The carbon dioxide formed inreactor 123 is converted to carbon monoxide by contact with coal inchamber 92, thus making substantially complete utilization of the coaland of the oxygen of the system.

Reactor E23 may be positioned vertically, horizontally, or angularlywithout departing from the scope of this invention. It is preferred,however, to position elongated chamber 123 vertically using an upwardgas velocity therein above about 5 feet per second to move the coal andash in the direction of the gaseous stream.

The effluent from chamber 10i, such as that in conduit 103 or 104, maybe heat exchanged with the water in conduit 9S to utilize the heatcontent of. that stream. Various other process streams may be heatexchanged without departing from the scope of this invention. Chamber107i may also be operated similar to chamber 62 of Figure 2 in which thesolids move in the direction of flow of the gases. In such instance,separators, etc., must be provided for removing entrained solids asdescribed in Figure 2.

An important feature of the present invention is the introduction offresh solid carbon-containing materia into the system at any point atwhich conditions are best suited for the particular solid and thedesired results to be obtained. rvIhe point of introduction of thesolids, such as fresh coal, into the system `vill depend upon variousfactors such as the type of coal, i. e., the ash content and fusiontemperature thereof, Whether it is desirable to recover the volatilecomponents of the coal without substantial cracking and the particulartemperature prevailing at the point of introduction of the coal. EnFigure l, fresh coal is introduced into the inlet line 6 to partialcombustion chamber 7 and/or inlet line 16 of gasification chamber 1S. lnFigure 2, fresh coal is introduced into the high velocity outlet gasstream of gasification chamber 62 and/or into the gaseous eliiuent frompartial combustion chamber 72. ln Figure fresh coal is introduceddirectly into partial combustion chamber 92 and/ or gasification chamber1M. Several other modifications for introducing the coal may bepracticel. For example, Figure 4 of the drawings diagiarninaticallyillustrates a modification of the gasi'iication chamber, such as chamberl of Figure l, or chamber' 1&1; of Figure 3. According to themodification of Figure 4, numeral 131 indicates a cylindricalgas"ication chamber containing a lower pseudo-liquid dense phase 432 offinely-divided solids separated from an upper pseudo-liquid dense phase133 of fresh coal by means of a perforated plate or screen 134. Steam isintroduced into the lower portion of gasification chamber 131 throughconduit 136 and coal and/or coke in dense phase i332 is reacted withsteam to produce hydrogen and carbon monoxide. Entrained coal andreaction products comprising hydrogen and carbon monoxide pass upwardlythrough gasification chamber 131 through perforated plate 134 into thepseudo-liquid dense phase of fresh coal 133. Fresh coal is introducedinto upper dense phase 133 by means of conduit 137 in the top of chamber131. The gaseous effluent passing through dense phase 133 is at theminimum temperature for the process and at this temperature the volatilecomponents of the coal are distilled from the coal. A gaseous eiiiuentpasses from dense phase 1.33 and is removed from gasification chamber3l. through outlet conduit 133. This gaseous effluent may be treated insubstantially the same manner as described with respect to Figure 3 inorder to separate and recover valuable volatile components of the coal.Coal or coke may be removed from upper dense phase i3?, and introducedinto lower dense phase L32 of gasification chamber 131 by means ofstandpipe l39 positioned within chamber 131. Alternatively oradditionally, coal or coke may be withdrawn directly from the densephase l33 of chamber it by means of outlet conduit M1 and passed to anyportion of the system desired, such as directly to a partial combustionchamber (not shown) for the conversion of the coal to carbon monoxide,or to dense phase T132. Also, coal may be removed from the lower densephase E32 of chamber 131 through a standpipe and may be passed orrecycled to a partial combustion chamber (not shown), or treated toremove ash ihere rom as described with respect to Figure 3. When coal ispassed directly from dense phase 133 to dense se i3?. substantially allof the coal is removed through duit 2 for recycling to a partialcombustion cham- Up .r and lower portions of chamber 131 including therespective dense phases of solids 132 and 133,

constructed as separate Zones suitably connected departing from thescope of this invention. A aerating or stripping gas may be introducedconduits E39, 141 and M2. Jure 5 represents another modification of thepresent invention which is particularly useful for the recovery o?volatile components of the coal with minimum contamination with thegaseous components hydrogen, carbon monoxide and carbon dioxide. In thismodification the size of equipment for recovering the volatilecomponents of the coal is minimized. According to the niodificzun shownin Figure 5, numeral 152 indicates a reaction chamber, either agasification chamber or a partial combustion chamber' as previouslydescribed. Reactants are introduced into chamber l5?. through inletconduit ll. A reaction effluent containing cntrained coal or colte isremoved from reaction chamber 152 through conduit 5.53 and is passed toa conventional solids separator 54. Hot coal or coke is separated fromtno reaction effluent in separator 154 and is passed through standpipeor conduit l5? to a volatilization chamber l5?. Vflic reaction effluentis removed from separator 154 through conduit 156.

in volatiization chamber 15% hot solids from chamber are admixed withfresh coal introduced therein through conduit itil. ln this manner thefresh coal is heated to a suhiciently high temperature to distill thevolatile components therefrom. An elluent comprising the volatilecomponents of the coal and substantially free from hydrogen, carbonmonoxide and carbon dioxide is removed from chamber l through outletconduit 159. Yfhis effluent may be passed to conventional separation andrecovery equipment (not shown) for the recover of the volatilecomponents of the fresh coal. A portion of the effluent in conduit 159is recycled through conduit tot in order to aid in maintaining the coalin chamber l5@ in an aerated or fluidized condition therein. Fresh coalmay conveniently be introduced into conduit 161 by means of conduit 162and thereby injected into chamber 153. The passage of a gas upwardlythrough chamber 353 intimately mixes the fresh coal with the hot solidsfrom chamber i221, thus maintaining substantial uniform temperatureconditions. Coal and/or coke may be intermittently or continuouslyremoved from chamber 158 through conduit 163 and passed to either agasification chamber or a partial combustion chamber (not shown), asdesired. lf the coal or colte removed from chamber SS through conduit163 is at a higher temperature than the temperature of the gasificationchamber, it is preferred to introduce the hot coal into the gasificationcharnber. However', if the coal or coke removed from chamber 158 is at alower temperature than the temperature of the gasification chamber ofthe system, it is best to pass the coal to the partial combustionchamber so that it may be heated prior to circulation to thegasification chamber.

Coal may be passed directly from chamber lSZ, such as from a dense phaseof rinely-divided coal thereinto material withdrawn from the reactionZones when coal is the feed material.

Various pumps, coolers, separators and auxiliary equipment have beeneliminated from the drawings as a matter of convenience and clarity andtheir use and location will become apparent to those skilled in the art.Various alterations and modifications of the present invention willbecome apparent to those skilled in the art without departing from thescope of this invention.

Having described our invention, we claim:

l. A process for producing a gaseous mixture of hydrogen and carbonmonoxide which comprises passing steam and iinely-dividedcarbon-containing material through a rst reaction zone at a velocityeiective to move said finely-divided carbon-containing material as afluidized mass through said rst reaction zone in the direction of flowof the gases therethrough, mainand about l700 F. such that hydrogen andcarbon monoxide are produced as the principal products of the reactionbetween steam and carbon, withdrawing an efHuent from said rst reactionzone comprising hydrogen, carbon monoxide, entrained ash and unconvertedcarbon-containing material and passing same at a relatively highvelocity of at least feet per second to a solids separator in whichsolids are separated from the euent, fresh carbon-containing materialzone, passing pure oxygen upward through said second reaction zone at avelocity such that nely-divided solids are maintained in a pseudo-liquidfluidized condition therein, maintaining said second reaction zone underexothermic conditions of reaction at a temperature between about 1800and about 2000 F. such that a product gas containing a major amount ofcarbon monoxide and a minor amount of less than about 1% carbon dioxideis produced, the reaction conditions in said second reaction zone havean over-all exothermic eect such that moving a suicient quantity offinely-divided solids from said second reaction zone substantially atthe temperature of said second reaction zone and passing same to saidrst reaction zone to maintain the temperature therein in the aboverange.

2. A process for producing a gaseous mixture of hydrogen and carbonmonoxide which comprises passing steam and finely-dividedcarbon-containing material through a rst reaction zone at a velocityeffective to move said finely-divided carbon-containing material as auidized mass through said first reaction zone in the direction `of ilowof the gases therethrough, maintaining in said first reaction zoneendothermic conditions of reaction and a temperature between about 1300and about l700 F. such that hydrogen and carbon monoxide monoxide whichcomprises passing steam and finely-divided carbon-containing materialthrough a first reaction zone at a velocity effective to move saidfinely-divided carbon-containing material as a iiuidized mass throughsaid rst reaction zone in the direction of ow changing the aforesaidoxygen and steam bined eluents prior to charging the same to thereaction 15 zones in the aforesaid manner, and removing a sufficientquantity of finely-divided solids from said second reaction zonesubstantially at the temperature of said second reaction zone andpassing same to said first reaction zone to maintain the temperaturetherein in the above range.

4. A process for producing a gaseous mixture cornprising hydrogen andcarbon monoxide which comprises supplying pure oxygen for passageupwardly through a mass of finely divided carbon containing solidmaterial in a first reaction Zone at a velocity effective to suspendsaid solids in a iiuidized condition, reacting a portion of the carboncontaining solids with oxygen containing gas in the first reaction zoneat a temperature of about 1800 to about 2000* F. thus producing aproduct gas containing a major amount of carbon monoxide and a minoramount of less than about 1% carbon dioxide, the reaction conditions insaid first reaction Zone have an overall exothermic effect such that noexternal source of heat is necessary to maintain the aforesaidtemperature therein, passing steam upwardly through a mass of finelydivided carbon containing solid material in a second reaction zone at avelocity effective to suspend said solids in a iiuidized condition,reacting the solids and steam in the second reaction zone at atemperature of about 1300 to about 1700 F. thus producing carbonmonoxide and hydrogen as the principal products of the reaction,withdrawing a portion of carbon containing solids from the firstreaction zone and passing same to the second reaction zone wherein thereaction conditions produce endothermie heat effects in a quantitysufficient to maintain the aforesaid temperature therein, separatelyremoving efliuents from said first and second reaction zones as theproduct of the process containing entrained finely divided ash andunconverted carbon containing material, passing said separate effluentsto a common solids separating Zone wherein the effluents are combinedand the ash and carbon material are removed from the emuents, and heatexchanging the aforesaid oxygen stream and steam with the combinedeffluents prior to charging the same to the reaction zones in theaforesaid manner.

5. A process for producing a gaseous mixture comprising hydrogen andcarbon monoxide which comprises supplying pure oxygen for upward flowthrough a mass of finely divided carbon containing solid material in afirst reaction zone at a velocity effective to suspend the solids in auidized condition, reacting a portion of the carbon containing solidswith oxygen in the first reaction zone at a temperature of about 180()oto about 2000" F. thus producing a product gas containing substantiallyall carbon monoxide and less than about 1% carbon dioxide, the reactionconditions in said first reaction zone have an overall exothermie effectsuch that no external source of heat is required to maintain theaforesaid temperature therein, passing steam upwardly through a mass offinely divided carbon containing solid material in a second reactionzone at a velocity effective to suspend said solids in a fiuidizedcondition, reacting the solids and steam in the second reaction zone ata temperature of about l500 to about i700 F. thus producing principallycarbon monoxide and hydrogen and less than about 5% of carbon dioxide,methane and water in the reaction product effluent, withdrawing aportion of carbon containing solids from the first reaction zone andpassing same to the second reaction zone wherein the reaction conditionsproduce endothermic heat effects in a. quantity sufficient to maintainthe aforesaid temperature therein, separately removing efliuents fromsaid first and second reaction zones as the product of the processcontaining entrained finely divided ash and unconverted carboncontaining material, passing said separate efliuents to a common solidsseparating zone wherein the eflluents are combined and the ash andcarbon material are removed from the effluents, and heat exchanging theaforesaid oxygen stream and steam with the combined CTI effluents priorto charging same to the reaction zones in the aforesaid manner.

6. A process for producing a gaseous mixture cornprising hydrogen andcarbon monoxide which comprises supplying pure oxygen for passageupwardly through a mass of finely divided carbon containing solidmaterial in a rst reaction Zone at a velocity effective to suspend thesolids in a fiuidized condition, reacting a portion of the carboncontaining solids with the oxygen in the first reaction zone at atemperature of about 1800 to about 2000" F. thus producing a product gascontaining a major amount of carbon monoxide and a minor amount of lessthan about 1% carbon dioxide, the reaction conditions in said reactionZone have an overall exothermic effect such that no external source ofheat is necessary to maintain the aforesaid temperature therein, passingsteam upwardly through a mass of finely divided carbon containsolidmaterial in a second reaction zone at a velocity effective to suspendsaid solids in a fiuidized condition, reacting the solids and steam inthe second reaction zone at a temperature of about 1300" to about 1700F. thus producing a major amount of carbon monoxide and hydrogen and aminor amount of carbon dioxide, withdrawing a portion of carboncontaining solids from the first reaction zone and passing same to thesecond reaction zone wherein the reaction conditions produce endothermicheat effects in a quantity sufficient to maintain the temperaturetherein, passing the effluent comprising carbon monoxide, carbon dioxideand hydrogen from the second reaction Zone to a carbon dioxide absorberin which the carbon dioxide is removed therefrom, recycling the carbondioxide thus removed to the first reaction Zone for conversion to carbonmonoxide, combining the effluent from the second reaction Zonesubstantially free of carbon dioxide and the effluent comprising carbonmonoxide from the first reaction Zone as the product of the process andheat exchanging the aforesaid oxygen stream and steam with the combinedeffluents prior to charging the same to the reaction Zones in theaforesaid manner.

7. A process for producing a gas of relatively high heat valuecomprising hydrogen, carbon monoxide and methane from coal whichcomprises supplying pure oxygen for passage upwardly through a mass offinely divided carbon-containing material in a first reaction Zone at avelocity effective to suspend said coal in a uidized condition, reactinga portion of the carbon with the oxygen in the first reaction zone at atemperature of about l800 to about 2000" F. thus producing a product gascontaining a major amount of carbon monoxide and a minor amount of lessthan about 1% carbon dioxide, the reaction conditions in said firstreaction zone have an overall exothermic effect such that no externalsource of heat is necessary to maintain the aforesaid temperaturetherein, passing steam upwardly through a mass of finely divided carboncontaining material in a second reaction Zone at a velocity effective tosuspend said carbon-containing material in a fiuidized condition,reacting the carbon and steam in the second reaction zone at atemperature of about 1300 to about l500 F. thus producing hydrogen,carbon monoxide, methane and carbon dioxide as the principal products ofthe reaction, withdrawing a portion of finely divided solids from thefirst reaction zone and passing same to the second reaction zone whereinreaction conditions produce endothermic heat effects in a quantitysufficient to maintain the aforesaid temperature therein, introducingfresh coal into a second reaction zone whereby the volatile componentsof said coal are distilled, removing an effluent comprising hydrogen,carbon monoxide, methane, carbon dioxide and volatile components of thecoal from the second reaction zone, condensing the normally liquidvolatile components of the coal from the effluent from the secondreaction zone, passing the remainder of the effluent from the secondreaction zone substantially free of normally liquid volatile componentsto a carbon dioxide absorber wherein carbon dioxide is same to thereaction zones in the aforesaid manner.

8. A process for producing a gas of relatively high heating valuecomprising hydrogen, carbon monoxide and methane from coal whichcomprises supplying pure oxygen for passage upwardly through a vmass ofiinely divided carbon-containing material in a first reaction zone at avelocity effective to suspend the carbon-containing materal in ailuidized condition, reacting a portion of carbon with the oxygen in thefirst reaction zone at a temperature of about 1800 to about 2000 F. thusproducinga product gas containing a major amount of carbon monoxide anda minor amount of less than about 1% carbon dioxide, the reactionconditions in said first reaction zone have an overall exothermic effectso that no external source of heat is necessary to maintain theaforesaid temperature therein, passing steam upwardly through a mass offinely divided carbon-containing reaction zone at a velocity effectiveto suspend the carboncontaining material in a fluidized condition,reacting the carbon and steam in the second reaction Zone at atemperature of about 1300 to about l500 F. thus producing hydrogen,carbon monoxide, methane and carbon dioxide as the principal products ofthe reaction, withdrawing a portion of nely divided solids from the rstreaction zone and passing same to the second reaction zone wherein thereaction conditions produce endothermic heat effects in a quantitysuiiicient to maintain the aforesaid temperature therein, removing aneliiuent comprising hydrogen, cardioxide from the reaction zone to acarbon dioxide absorber wherein the carbon dioxide is separated from theelluent and recovered, passing the recovered carbon dioxide to the irstreaction zone wherein it is converted to carbon monoxide, and combiningthe eiliuent comprising hydrogen, methane and carbon monoxide from thesecond reaction zone substantially free of carbon dioxide with theeffluent comprising carbon monoxide from the rst reaction zone as theproduct of the process and heat exchanging the aforesaid oxygen andsteam with the combined efliuents prior to charging the same to thereaction zones in the aforesaid manner.

9. A process for the gasification of coal and the recovery of volatilecomponents therefrom which comprises supplying pure oxygen for passageupwardly through a mass of iinely divided carbon containing solidmaterial in a iirst reaction zone at a velocity effective to suspend thesolids therein, reacting a portion of the carbon with the oxygen in theiirst reaction zone at a temperature of about l800 to about 2000 F.suitable for the production of a product gas containing a major amountof carbon action zone have an overall exothermic effect such that noexternal heat is necessary to maintain the required temperature therein,simultaneously passing steam upwardly through a mass of finely dividedcarbon containing solid material in a second reaction zone at a velocityeffective to suspend the solids therein, reacting steam with part of thecarbon material in the second reaction lzone at a temperature of about1300 to about 1700 F. suitable for producing principally carbon monoxideand hydrogen, passing the eiuent from the second reaction zone upwardlythrough a mass of iinely divided coal in a ldistillation zone at avelocity eifective to suspend the coal in a iluidized condition,circulating finely divided solids bedistilled, passing finely dividedcarbon containing material to about 1700 F. oxide and hydroxen asreaction, the reaction conditions in the second reaction tion zone tomaintain the solids therein in an aerated iinely dividedcarbon-containing masame to the reaction zones in the aforesaid manner.

11. A process for producing normally liquid organic compounds from coalwhich supplying pure oxygen for zone at a temperature of about l800 toabout 2000 F. thus producing a product gas containing a major amount ofcarbon monoxide and a minor amount of less than about 1% carbon dioxide,the reaction conditions in the first reaction zone have an overallexothermic effect such that no external source of heat is necessary tomaintain the aforesaid temperature therein, passing steam upwardlythrough a mass of finely divided carbon-containing material in a secondreaction zone at a velocity effective to suspend the finely dividedmaterial in a fluidized condition, reacting the steam and carbon in thesecond reaction zone at a temperature of about 1500 to about 1700 F.thus producing hydrogen and carbon monoxide as the principal products ofthe reaction, circulating finely divided solid material between saidreaction zones to maintain the temperatures therein within the aforesaidranges, separately removing effluents from said first and secondreaction zones containing entrained finely divided ash and unconvertedcarbon containing material, passing said separate effluents to a commonsolids separator in which the effluents are combined and ash and carboncontaining materials are removed from the eflluents, heat exchanging theaforesaid oxygen and steam with the combined effluents prior to chargingthe same to the reaction zones in the aforesaid manner, passing saidcombined effluents after heat exchange with said oxygen and steam to asynthesis reaction zone in which hydrogen and carbon monoxide areconverted to normally liquid organic compounds, removing an effluentcomprising normally liquid organic compounds, methane and carbon dioxidefrom said synthesis reaction zone, separating normally liquid organiccompounds from the eflluent of said synthesis reaction zone as theproduct of the process, separating the carbon dioxide from the normallygaseous components of said eluent from said synthesis reaction Zone,passing the carbon dioxide thus separated to the said first reactionzone, and passing normally gaseous components of said effluent from saidsynthesis reaction zone substantially free from carbon dioxide to saidsecond reaction Zone.

l2. A process for producing normally liquid organic compounds fromcarbon containing solid materials which comprises supplying pure oxygenfor passage through a mass of finely divided carbon containing solidmaterial in a first reaction zone at a velocity effective to suspend thesolid material therein, reacting part of the carbon with oxygen in thefirst reaction zone at a temperature of about 1800 to about 2000 F. thusproducing a product gas containing a major amount of carbon monoxide anda minor amount of less than about 1% carbon dioxide, passing steamthrough a mass of finely divided carbon containing solid material in asecond reaction zone at a velocity effective to suspend the carbonmaterial therein, reacting carbon with steam in the second reaction zoneat a temperature of about 1500 to about 1700 F. thus producing hydrogenand carbon monoxide as the principal products of the reaction,withdrawing a portion of the finely divided solids from the firstreaction zone and passing same to the second reaction zone wherein thereaction conditions produce endothermic heat effects in a quantitysufficient to maintain the desired temperature therein, separatelyremoving effluents from said first and said second reaction zones andcombining same, heat exchanging the aforesaid oxygen and steam with thecombined effluents prior to passing the same to the reaction zones inthe aforesaid manner, passing said combined effluents to a synthesisreaction zone in which hydrogen and carbon monoxide are converted tonormally liquid organic compounds, removing an effluent comprisingnormally liquid organic compounds, methane and carbon dioxide from theeffluent of said synthesis reaction zone as a product of the process,separating 'the carbon dioxide from the normally gaseous components ofsaid effluent from said synthesis reaction zone, and passing the carbondioxide thus separated to said first reaction Zone.

13. A process for producing normally liquid organic compounds fromcarbon containing solid material which comprises supplying pure oxygenfor passage through carbon containing solid material in a first reactionzone, reacting part of the carbon with the oxygen in the first reactionzone at an elevated temperature about 1800 to 2000 F. suitable forproducing a product gas containing a major amount of carbon monoxide anda minor amount r. l.. I si prising carbon of less than about 1% carbondioxide, the reaction conditions in the first reaction Zone are suchthat an overall exothermic heat effect is produced, passing steamthrough a mass of carbon containing solid material in a second reactionzone under conditions including a temperature of about 1300" to 1700 F.suitable for producing hydrogen and carbon monoxide as the principalproducts of the reaction, the reaction conditions in the second reactionzone are such that an overall endothermic heat effect is produced,transferring the exothermic heat produced in the first zone to thesecond reaction zone by passing finely divided carbon-containingmaterial from the former zone to the latter Zone in order to maintainthe desired temperature therein, separately removing eflluents from saidfirst and said second reaction zones and combining same, heat exchangingthe oxygen and steam with the combined effluents prior to passing thesame to the reaction Zones in the aforesaid manner, passing saidcombined eflluents to a synthesis reaction Zone in which hydrogen andcarbon monoxide are converted to normally liquid organic compounds,removing an effluent comprising normally liquid organic compounds,methane and carbon dioxide from said synthesis reaction Zone, separatingnormally liquid organic compounds from the effluent of said synthesisreaction zone as a product of the process, and passing normally gaseouscomponents of said effluent containing carbon dioxide from saidsynthesis reaction Zone to said first reaction zone.

14. A process for producing a gaseous mixture comprising carbon monoxideand hydrogen which comprises supplying pure oxygen for passage upwardlythrough a mass of ash-producing finely divided carbon containing solidmaterial in a first reaction zone at a velocity effective to suspend thesolids in a fluidized condition, reacting a portion of carbon containingsolids with oxygen in the first reaction Zone at a temperatui'e of about1800 to about 2000 F. thus producing a product gas containing a majoramount of carbon monoxide and a minor amount of less than about 1%carbon dioxide, the reaction conditions in said first reaction zone havean overall exothermic effect such that no external source of heat isnecessary to maintain the aforesaid temperature therein, passing steamupwardly through a mass of ash-producing finely divided carboncontaining solid material in a second reaction zone at a velocityeffective to suspend the solids in a fluidized condition, reacting thesteam and part of the solid material in the second reaction zone at atemperature of about 1300 to about 1700 F. thus producing principallycarbon monoxide and hydrogen, withdrawing a portion of solid materialfrom the first reaction zone and passing same to the second reactionzone wherein the reaction conditions produce endothermic effects in aquantity sufficient to maintain the desired temperature in the secondreaction zone, withdrawing a portion of finely divided solid materialincluding carbon from the second reaction zone and passing same to athird reaction zone wherein the carbon is reacted with oxygencoritaining gas and completely converted to an effluent commonoxide,carbon dioxide, unreacted oxygen and finely divided ash, the quantity ofsolid material withdrawn from the second reaction zone and passed to thethird reaction zone is suflicient to prevent substantially ash build-upin the system, separating the ash from the eflluent of the thirdreaction zone and discharging the same from the system, recycling theeffluent containing carbon dioxide and substantially free of ash to thefirst reaction Zone, separately removing effluents from the first andsecond zones and combining same as the prod-- uct of the process andheat exchanging the aforesaid oxygen and steam with the combinedeffluents prior to charging the same to the reaction zones in theaforesaid manner.

15. The process of claim 4 wherein fresh coal is charged to the firstreaction zone.

2,713,590 21 22 16. The process of claim 4 wherein fresh coal is2,472,219 Lyons June 7, 1949 charged to the second reaction zone.2,482,187 Johnson Sept. 20, 1949 2,499,372 DOuville Mar. 7, 1950References Cited in the file 0f this patent 2,521,195 Wheeler, Jr. Sept.5, 1950 5 2,560,403 Arveson July 10, 1951 UNITED STATES PATENTS2,579,398 Roetheli Dec. 18, 1951 1,992,909 DaVS Feb. 26, 1935 2,588,076Gohr Mar. 4, 1952 2,176,441 Ulrich et al. Oct. 17, 1939 2,436,938scharmann et a1. Mar. 2, 1948 FOREIGN PATENTS 2,445,327 Keith July 20,1948 10 582,055 Great Britain Nov. 4, 1946 2,460,508 Johnsofr- Feb. 1,1949 586,391 Great Britain Mar. 18, 1947

11. A PROCESS FOR PRODUCING NORMALLY LIQUID ORGANIC COMPOUNDS FROM COALWHICH COMPRISES SUPPLYING PURE OXYGEN FOR PASSAGE UPWARDLY THROUGH AMASS OF FINELY DIVIDED CARBON-CONTAINING MATERIAL AT A VELOCITYEFFECTIVE TO SUSPEND THE SAME IN A FLUIDIZED CONDITION, REACTING PART OFTHE CARBON WITH THE OXYGEN IN THE FIRST REACTION ZONE AT A TEMPERATUREOF ABOUT 1800* TO ABOUT 2000* F. THUS PRODUCING A PRODUCT GAS CONTAININGA MAJOR AMOUNT OF CARBON MONOXIDE AND MINOR AMOUNT O LESS THAN ABOUT 1%CARBON DIOXIDE, THE REACTION CONDITIONS IN THE FIRST REACTION ZONE HAVEAN OVERALL EXOTHERMIC EFFECT SUCH THAT NO EXTERNAL SOURCE OF HEAT ISNECESSARY TO MAINTAIN THE AFORESAID TEMPERATURE THEREIN, PASSING STEAMUPWARDLY THROUGH A MASS OF FINELY DIVIDED CARBON-CONTAINING MATERIAL INA SECOND REACTION ZONE AT A VELOCITY EFFECTIVE TO SUSPEND THE FINELYDIVIDED MATERIAL IN A FLUIDIZED CONDITION, REACTING THE STEAM AND CARBONIN THE SECOND REACTION ZONE AT A TEMPERATURE OF ABOUT 1500* TO ABOUT1700* F. THUS PRODUCING HYDROGEN AND CARBON MONOXIDE AS THE PRINCIPALPRODUCTS OF THE REACTION, CIRCULATING FINELY DIVIDED SOLID MATERIALBETWEEN SAID REACTION ZONES TO MAINTAIN THE TEMPERATURES THEREIN WITHINTHE AFORESAID RANGES, SEPARATELY REMOVING EFFLUENTS FROM SAID FIRST ANDSECOND REACTION ZONES CONTAINING ENTRAINED FINELY DIVIDED ASH ANDUNCOVERTED CARBON CONTAINING MATERIAL, PASSING SAID SEPARATE EFFLUENTSTO A COMMON SOLIDS SEPARATOR IN WHICH THE EFFLUENTS ARE COMBINED AND ASHAND CARBON CONTAINING MATERIALS ARE REMOVED FROM THE EFFLUENTS, HEATEXCHANGING THE AFORESAID OXYGEN AND STEAM WITH THE COMBINED EFFLUENTSPRIOR TO CHARGING THE SAME TO THE REACTION ZONES IN THE AFORESAIDMANNER, PASSING SAID COMBINED EFFLUENTS AFTER HEAT EXCHANGE WITH SAIDOXYGEN AND STEAM TO A SYNTHESIS REACTION ZONE IN WHICH HYDROGEN ANDCARBON MONOXIDE ARE CONVERTED TO NORMALLY LIQUID ORGANIC COMPOUNDS,REMOVING AN EFFLUENT COMPRISING NORMALLY LIQUID ORGANIC COMPOUNDS,METHANE AND CARBON DIOXIDE FROM SAID SYNTHESIS REACTION ZONE, SEPARATINGNORMALLY LIQUID ORGANIC COMPOUNDS FROM THE EFFLUENT OF SAID SYNTHESISREACTION ZONE AS THE PRODUCT OF THE PROCESS, SEPARATING THE CARBONDIOXIDE FROM THE NORMALLY GASEOUS COMPONENTS OF SAID EFFLUENT FROM SAIDSYNTHESIS REACTION ZONE, PASSING THE CARBON DIOXIDE THUS SEPARATED TOTHE SAID FIRST REACTION ZONE, AND PASSING NORMALLY GASEOUS COMPONENTS OFSAID EFFLUENT FROM SAID SYNTHESIS REACTION ZONE SUBSTANTIALLY FREE FROMCARBON DIOXIDE TO SAID SECOND REACTION ZONE.